Water-soluble cationic azo dyestuffs



United States Patent O 3,351,579 WATERSOLUBLE CATIONIC AZO DYESTUFFS Edwin Baier, Frankfurt am Main, Germany, assignor to Farbwerke Hoechst Aktieugesellschaft vorrnals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Oct. 1, 1963, Ser. No. 312,865 Claims priority, application Germany, Oct. 3, 1962, F 37,956 2 Claims. (Cl. 260-158) The present invention is concerned with water-soluble cationic dyestuffs and a process for preparing them; it relates especially to water-soluble cationic dyestuffs of the following general Formula 1 in which F represents the radical of a monoor disazodyestuif molecule, which does not contain any ionic groups imparting solubility in water, R represents an alkylene group, R and R each represent an alkyl group, Z

represents an anion and It stands for an integer from 1 to 2.

It has been found that water-soluble cationic dyestuffs- (obtainable by hydrolyzing a dyestutf of the following formula OCH;

3,351,579 Patented Nov. 7, 1967 into a mixture of an alkylating agent with an organic solvent, for example dimethyl formamide, benzene, toluene, or nitrobenzene, and reacted therein for 1 to 3 hours at a temperature within the range of about 80 to 120 C., preferably at about 100 C.

The dyestuffs corresponding to general Formula 2 indicated above, which are used as starting compounds, can be prepared by subjecting the corresponding dyestuffs which have the following general Formula 4 to a hydrolysis in an acid medium or by splitting the corresponding dyestuffs of the following general Formula 5 in an alkaline medium. The dyestuffs of Formula 5 can be prepared, for example, by coupling diazotized 4- arninobenzene sulfonyl amino ethyl-isothiuronium salts which are obtainable by the addition of thiourea to 4 amino benzene-sulfethylene-imide in an acid medium, with coupling components that do not contain any group imparting solubility in water.

The dyestuffs according to the invention are obtained in a good to very good yield and can; well be used for dyeing animal or vegetable fibrous materials. The dyeings produced on the said materials are distinguished by good wet-fastness properties and clear brilliant tints.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

EXAMPLE 1 15 parts of the azodyestuif of the following formula (JO-CH3 in an alkaline medium, the last-mentioned dyestuff being obtainable by coupling diazotized 4-amino-benzene-sul- NHg omo-Qmuc 0(|JHN=N-S 02-NH-om om s-o =mn 0 H56 0 o 9 CO-CH3 9 .F(- SO -NH-R-SH),, in which E R and have thvmeanings given above, in fonyl-aminoethyl-isothiuronium acetate with N-acean aqueous alkaline solution, suitably in an aqueous sodium hydroxide solution, with an alkylating agent, to yield the corresponding dyestuif thioether of the following general Formula 3 in which F, R, R and n have the meanings given above, drying the resulting compound and reacting it again with an alkylating agent.

The reaction of the starting dyestutf of general Formula 2 given-above with an alkylating agent, for example methyl iodide, dimethyl sulfate or diethyl sulfate, in an aqueous alkaline solution is suitably carried out at a temperature within the range of about to 80 C. The dyestutf thioether thus obtained is separated from the aqueous phase, washed with water until neutral and dried, the drying being suitably carried out at a temperature within the range of about 40 to 100 C. The dyestufi" thioether which has thus been freed from water is introduced, while stirring, into the alkylating agent or toacetyl 4 amino 1,3 dimethoxy-benzene, the said diazotized 4 amino benzene sulfonyl aminoethylisothiuronium acetate being obtainable by the addition reaction of thiourea with 4 aminobenzene sulfethylene irnide in an acetic acid medium) were dissolved in parts by volume of 2 Nsodium hydroxide solution.

15 parts of dimethyl sulfate were introduced, while stirring, at 60 C. into the solution that had been prepared. After the introduction was terminated stirring was continued for 1 hour at 60 C. and then for another 30 minutes at 70 C. The dyestuff thioether that had precipitated was filtered off, washed with hot water until neutral and dried at 80 C.

8 parts of the water-insoluble dyestuff thioether so obtained were slowly introduced at 80 C. into 30 parts of dimethyl sulfate. After the addition was terminated the reaction mixture was stirred for 3 hours at 80 C., then cooled to room temperature and mixed with 400 parts by volume of isopropanol.

The dyestuff that had precipitated was filtered off, dissolved in 200 parts by volume of water and precipitated 3 with 6 parts of sodium chloride. The resulting cationic introduced at 60 C., whilg stirring, into the solution dyestulf of the formula that had been prepared. After the introduction was ter- OCH;

CH3 CH3 Ol-IgO- N1-I-C -cH-N=N-so2l I-om-Cmg-om CI'I3O-SO39 was an oragne-colored powder which dissolved well in minated stirring was continued for 1 hour at 60 C. and water and dyed animal and vegetable fibrous materials then for another minutes at 70 C. The dyestuff thiobrilliant yellow tints. The dyeings produced with this dyeether that had formed and precipitated was filtered olf, stuit had good wet-fastness properties. washed with hot water until neutral and dried at 80 C. EXAMPLE 2 9 parts of the water-insoluble dyestuff thioether thus I 15 obta'ned Wer rea t dfo lh t10 4 12 parts of the disazodyestuff of the formula 1 e c e r our a 0 C with 0 parts were dissolved in 80 parts by volume of 2 N-sodium hyof dimethyl sulfate. The reaction mixture was then aldroxide solution. (This dyestuff is obtainable by subjecting lowed to cool and 200 parts by volume of isopropanol adyestufi of the formula were added. The dyestutf that had formed and precipito a hydrolysis in an alkaline medium, the last-mentioned tated was filtered off, washed with isopropanol and dried dyestuff being obtainable by coupling 2 mols of diazoat C. tized 4-amino-benzene-sulfonyl-aminoethyl-isothiuronium The cationic dyestuff of the formula CI-IaCOCH-CONH l l s H N H I N (1H3 (1H3 l (3H3 so-N-on-onz-scn3:\oH3-oso; SOzNCIIzCl-I -SBCH eu o-S0 acetate which may be prepared by the addition reaction of so obtained was a brown powder which dissolved well in thiourea with 4-aminobenzene-sulfethylene-imide in an water and dyed animal and vegetable fibrous materials acetic acid medium, with 1 mol of 2.6-bis-(aceto-acetylclear greenish yellow tints. The dyeings produced'with amino)-benzothiazole). 15 parts of dimethyl sulfate were this dyestufl had good wet-fastness properties.

I claim: 1. Dyestufi of the formula (I311: |CH3 0H30- NH-c 0- H-N=N-S 0 Q-N-CHFOIIQ- s -cm 01130301 COOHs 2. Dyestuff of the formula COCHa References Cited UNITED STATES PATENTS 2,201,814 5/1940 Evans et a1. 260609 FOREIGN PATENTS 1,240,748 8/1960 France.

CHARLES B. PARKER, Primary Examiner. D. PAPUGA, Assistant Examiner. 

1. DYESTUFF OF THE FORMULA 